| In this work,a series of coordination polymers(CPs)based on two semirigid tetracarboxylic acid ligands and three flexible tripodal ligands,with transition metal ions have been synthesized by solvothermal reactions.The control of the structure by varying factors is researched,and their topological structures,magnetic properties and photoluminescence are discussed in detail.1.The evolution of coordination polymers(CPs),the different factors influencing on the structures of CPs and the potential applications of CPs are outlined,respectively.2.Eight novel coordination polymers derived from the 3-(3',5'-dicarboxylphenoxy)phthalic acid(H4L1)and 3-(3',5'-dicarboxylphenoxy)phthalic acid(H4L2)ligand have been constructed under the similar synthesized conditions with Co(?)and Ni(?)ions in the presence of N-donor ancillary ligands(4,4'-bipy,dpa,4,4'-bibp,dib and bix),namely,[Co2(HLi)(4,4'-bipy)(?3-OH)(?2-H20)]n(1),[Co2(Li)(dpa)2]n(2),{[Co2(L1)(4,4'-bibp)(H20)4]·H20}n(3),[Co2(L1)(dib)2]n(4),[Co2(L1)(bix)1.5]n(5),{[Co4(L1)(4,4'-bibp)3]·(4,4'-bibp)3}n(6),[Ni2(HL1)(4,4'-bipy)(?3-OH)(?2-H2O)]n(7),[Co2(L2)(4,4'-bibp)2]n(8).Complex 1 possesses a(3,8)-connected tfz-d 3D structure containing[Co4(?3-OH)2(?2-H2O)2(COO)4]2+ secondary building units(SBUs)with a Schlafli symbol of(43)2(46.618.84).Complex 2 presents a 4-connected uninodal 3D framework and forming a 2-fold interpenetrating sod topology with a Schlafli symbol of(42.64).Complex 3 have 2D double layer networks and exhibits a 2D?3D framework through H-bonding interactions,which is a(3,3,4)-connected structure with a Schlafli symbol of(63.83)(63)(83).Complex 4 shows a 4-connected Nbo topology with point symbol of {64.82},which contains right-and left-handed helix chains formed by the connection of Co(?)and dib.Complex 5 displays a(4,4,5)-connected structure,possessing syn-anti carboxylate bridges metal units with a Schlafli symbol of(4.5.6.83)(42.53.6)(43.53.62.72).Complexes 1-5 show 3D structures with different topologies and different magnetic properties,exploring the effect of N-donor ligands on the target CPs.Complex 6 features a(4,8)-connected 3D framework with a Schlafli symbol of(3.44.6)(32.44.56.63),by comparing with 3,exploring the ratio of reactants impact on the target CPs.Complex 7 have completely the same framework with complex 1.Complex 8 derived from H4L2 with the same condition of 3 and 6,which obtained a new structure and have no affected by ratio of reactants.Complexes 1-8 show 3D structures with different topologies and different magnetic properties,exploring the effect of N-donor ligands,metal ions and ratio of reactants on the target CPs.3.Six new complexes based on H4L1,namely,[Zn2(Li)(H2O)3]n(9),{[Zn2(L1)(4,4'-bipy)(H20)2]·H2O}n(10),[Cd2(L1)(phen)]n(11),[Zn2(L1)(dib)(H20)2]n(12),[Zn2(Li)(bix)i.5]n(13),{[Cd2(Li)(bix)0.5(H2O)]·2H2O}n(14)have been constructed under the similar synthesized conditions with Zn(II)and Cd(II)ions in the presence or not of N-donor ancillary ligands(4,4'-bipy,phen,dib and bix).Complex 9 was obtained by H4L1 and Zn(II)without employing N-donor ancillary ligands and 2D structure was extended to a 3D framework by H-bonds,displaying a(3,4,6)-connected topology with a Schlafli symbol of(42.5)2(43.52.7)(45.56.63.7)2.Complex 10 can be regard as a(3,4,6)-connected 3,4,6T53 topology with a Schlafli symbol of(4.62)2(42.64)2(42.68.82.103).Complex 11 have 2D double layer networks,which extended to a 3D supermolecular framework by ?…? stacking interactions.Complex 12 possesses a(3,4,6)-connected topology with a Schlafli symbol of(4.102)(4.6.84)(62.8).Complexes 13 and 14 were employing the same N-donor ancillary ligands(bix),and got different structures with Zn(?)and Cd(?)ions,respectively.Complex 13 possesses a(4,4,5)-connected topology with a Schlafli symbol of(4.5.6.83)(42.53.6)(43.53.62.72).Complex 14 possesses a(3,8)-connected tfz-d topology with a Schlafli symbol of(43)2(46.618.84),the conformations of bix are varied.The photoluminescence properties of the ligands and the complexes 9-14 were investigated,the complex 14 have strong emission and have recognition capacity for Fe3+.4.Synthesis of three flexible tripodal ligands:1,3,5-[4-(4-pyridinol-methylene)]benzene(L3),1,3,5-[1-(2-methylimidazole-methylene)]benzene(L4),1,3,5-[4-(1-carboxyl-phenoxymethyl)]benzene(H3L5).Using solvothermal method,constructed seven new complexes 15-21:[Cd(L3)(NO3)2]n(15),{[Cd(L3)(NO3)2]·(CH3CH2OH)3}n(16),[Cd3(L4)2(m-BDC)(NO3)4]n(17),[Zn3(L4)(m-BDC)3]n(18),{[Ni(HL5)(dib)]·(H2O)2}n(19),{[Co(HL5)(dib)]·(H2O)2}n(20),[Mn(HL5)(4,4'-bipy)]n(21).Complexes 15 and 16 were synthesized in the same conditions by using acetonitrile an ethanol,respectively.Although they have the same cell parameters,the solvent molecular can only enter into the crystal lattice of 16,but not abserved in 15,possesses a 3-connected hcb 2D topology with a Schlafli symbol of(63).Complexes 17 and 18 were synthesized in the presence of isophthalic acid as ancillary ligands,and got different structures with Zn(?)and Cd(?)ions,respectively.17 has 2D wavelike grid layers and exhibits a 2D?3D framework through H-bonding interactions,possesses a(3,4,5)-connected fsc 2D topology with a Schlafli symbol of(44.610.8)(44.62)(412.82);18 shows larger pore feature and exhibits a 2D?3D framework through H-bonding interactions,possesses a(3,6)-connected 3,6L4 2D topology with a Schlafli symbol of(33)2(36.62.76.8)3.Complexes 19,20 and 21 were constructed by H3L5,which show the auxiliary ligand influence by comparing.19 and 20 are isomorphism,which have 3-fold interpenetrating 2D framework and expanded a 3D criss-cross construction structures due to ?…? stacking interactions,displays a hcb topology with a Schlafli symbol of(63).Complex 21 is 4-fold interpenetrating 3D framework with typical cage-like 2D structure,displays a 3,5L2 topology with a Schlafli symbol of(42.67.8)2(42.6). |
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